Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
  • F16L11/125—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
  • Y10T428/1393—Multilayer [continuous layer]

Definitions

• the invention relates to a multilayer structure, in particular in the form of a tube, and its use for transporting fluids, in particular gasoline-type fuel, in particular alcoholic, in particular for motor vehicles.
• the invention relates more particularly to the tubes present within an engine.
• These tubes can for example be intended for the transport of fuels, in particular between the tank and the engine, for the cooling circuit, for the hydraulic system, or for the air conditioning circuit or the transport of a mixture of urea and water. .
• the tubes used are manufactured by mono-extrusion, if it is a single-layer tube, or by co-extrusion of the different layers, if it is a multilayer tube, according to the techniques. usual processes for thermoplastics processing.
• the structures (MLT) for the transport of gasoline typically consist of a barrier layer such as EVOH, surrounded on both sides by a PA layer (at least one layer) and optionally comprising layers of binders in the case where the adhesion, between the other layers, proves insufficient.
• patent EP 2098580 describes in particular tubes having an EVOH barrier and at least two layers of polyamides, plasticized or not, one being located above the barrier layer and the other being located below the barrier layer.
• the present invention intends to solve this new problem by an arrangement and a particular constitution of the layers of the multilayer structure.
• fluid denotes a gas used in the automobile or a liquid, in particular a liquid and in particular an oil, a brake fluid, a urea solution, a glycol-based coolant, fuels, in particular.
• light fuels liable to pollute advantageously fuels except diesel, in particular gasoline or LPG, in particular gasoline and more particularly alcoholic gasoline.
• Air, nitrogen and oxygen are excluded from the definition of said gas.
• said fluid designates fuels, in particular gasoline, in particular alcoholic gasoline.
• gasoline denotes a mixture of hydrocarbons obtained from the distillation of petroleum to which additives or alcohols such as methanol and ethanol may be added, the alcohols possibly being the major components in certain cases.
• alcoholic gasoline denotes a gasoline to which methanol or ethanol has been added. It also designates a gasoline of type E95 which does not contain any petroleum distillation product.
• all the layers (2) and any other layers located below the barrier layer means all the layers present located below the barrier layer.
• barrier layer denotes a layer having characteristics of low permeability and of good resistance to the various constituents of fluids, in particular fuels, that is to say that the barrier layer slows down the passage of fluid, in particular fuel, both for its polar components (such as ethanol) and for its non-polar components (hydrocarbons) in the other layers of the structure or even outside the structure.
• the barrier layer is therefore a layer allowing above all not to lose too much gasoline in the atmosphere by diffusion, thus making it possible to avoid atmospheric pollution.
• barrier materials are chosen from polyphthalamides and / or copolymers of ethylene and of vinyl alcohol (denoted EVOH below).
• the EVOHs are particularly advantageous, in particular the richest in vivnyl alcohol comonomer as well as those modified impact because they make it possible to produce less fragile structures.
• the inventors have therefore found that the absence or at least a very small proportion of plasticizer in the inner layer (s), that is to say located under the barrier layer, made it possible to greatly reduce the proportion of extractables such as as determined by a test as defined above and in particular by a test which consists of filling a tubular structure with alcoholic gasoline type FAM-B and heating the assembly to 60 ° C for 96 hours, then emptying it by filtering it in a beaker, then allowing the filtrate from the beaker to evaporate at room temperature to finally weigh this residue, the proportion of which must be less than or equal to approximately 6 g / m2 of the internal surface of the tube.
• FAM B alcoholic gasoline is described in DIN 51604-1: 1982, DIN 51604-2: 1984 and DIN 51604-3: 1984.
• FAM A alcoholic gasoline is first prepared with a mixture of 50% Toluene, 30% isooctane, 15% di-isobutylene and 5% ethanol then FAM B is prepared by mixing 84.5% FAM A with 15% methanol and 0.5% water.
• FAB consists of 42.3% toluene, 25.4% isooctane, 12.7% di-isobutylene, 4.2% ethanol, 15% methanol and 0.5% water.
• said inner layer (2) comprising predominantly at least one polyamide of aliphatic type means that said polyamide of aliphatic type is present in a proportion of more than 50% by weight in layer (2).
• the polyamide of the aliphatic type is linear and is not of the cycloaliphatic type.
• said polyamide of predominantly aliphatic type of the layer or layers (2) also predominantly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer (s) (2) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer (s) (2) is completely aliphatic.
• PPAs are also of interest, in particular coPA6T, PA9T and its copolymers, PA10T and its copolymers.
• copolyamides in the broad sense, which although not preferred, falls within the scope of the invention.
• copolyamides comprising not only amide units (which will be in the majority, hence the fact that they are to be considered as copolyamides in the broad sense), but also units of a non-amide nature, for example ether units.
• the best known examples are PEBA or polyether-block-amide, and their copolyamideester-ether variants, copolyamide-ether, copolyamide ester.
• PEBA-12 where the polyamide units are the same as those of PA12
• PEBA-6.12 where the polyamide units are the same as those of PA6.12.
• Homopolyamides, copolyamides and alloys are also distinguished by their number of carbon atoms per nitrogen atom, knowing that there are as many nitrogen atoms as there are amide groups (-CO-NH-).
• a high carbon polyamide is a polyamide with a high ratio of carbon atoms (C) relative to the nitrogen atom (N). These are polyamides with approximately at least 9 carbon atoms per nitrogen atom, such as for example polyamide-9, polyamide-12, polyamide-11, polyamide-10.10 (PA10.10), copolyamide 12 / 10.T, copolyamide 11 / 10.T, polyamide-12.T, polyamide-6.12 (PA6.12). T represents terephthalic acid.
• a low carbon polyamide is a polyamide with a low ratio of carbon atoms (C) relative to the nitrogen atom (N). These are the polyamides with approximately less than 9 carbon atoms per nitrogen atom, such for example polyamide-6, polyamide-6.6, polyamide-4.6, copolyamide-6.T / 6.6, copolyamide 6.I /6.6, copolyamide 6.T / 6.I / 6.6, polyamide 9.T. I represents isophthalic diacid.
• PA6.12 is an PA with 9 carbon atoms per nitrogen atom, in other words a PA in C9.
• PA6.13 is in C9.5.
• the number of carbon atoms per nitrogen atom is calculated according to the same principle. The calculation is carried out on a molar basis for the various amide units. In the case of a copolyamide having units of non-amide type, the calculation is carried out only on the part of amide units.
• PEBA-12 which is a block copolymer of amide units 12 and ether units
• the average number of carbon atoms per nitrogen atom will be 12, as for PA12; for PEBA-6.12, it will be 9, as for PA6.12.
• high carbon polyamides such as polyamide PA12 or 11 adhere with difficulty to an EVOH polymer, to a low carbon polyamide.
• polyamide such as PA6, or on an alloy of polyamide PA6 and polyolefin (such as, for example, a Orgalloy ® marketed by Arkema).
• Bio-fuels are not only derived from petroleum but include a proportion of polar products such as alcohols of plant origin, such as ethanol or methanol, of at least 3%. This rate can go up to 85% or even 95%.
• the fuel circulation temperature tends to rise due to the new engines (more confined, operating at higher temperature).
• Said inner layer (2) or each of the layers (2) and of the other possible layers located below the barrier layer contains from 0 to 1.5% by weight of plasticizer relative respectively to the total weight of the composition of the layer (2) or to the total weight of each of the compositions of the layers (2) and of any other layers located below the barrier layer.
• said inner layer (2) or each of the layers (2) and any other layers located below the barrier layer is ( are) devoid of plasticizer.
• all the layers located under the barrier layer are completely devoid of plasticizer and constitute one of the preferred structures of the invention.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one more outer layer (3) located above the barrier layer is present, said outer layer (3) comprising mainly at least one polyamide of the aliphatic type or one consisting of more than 75% of aliphatic units, in particular said aliphatic polyamide having an average number of carbon atoms per nitrogen atom of between 9.5 and 18, advantageously from 11 to 18.
• MMT multilayer tubular structure
• said outer layer (3) comprising predominantly at least one polyamide of aliphatic type means that said polyamide of aliphatic type is present in a proportion of more than 50% by weight in layer (3).
• the polyamide of the aliphatic type is linear and is not of the cycloaliphatic type.
• said polyamide of predominantly aliphatic type of the layer or layers (3) also predominantly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer or layers (3) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer or layers (3) is completely aliphatic.
• said polyamide of predominantly aliphatic type of the layer or layers (2) and of the layer or layers (3) also predominantly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer (s) (2) and of the layer (s) (3) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer (s) ( 2) and the layer (s) (3) is completely aliphatic.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which said outer layer (3) comprises from 0 to 15% of plasticizer relative to the total weight of the composition of the layer (3). , or in which all of the outer layers comprise on average from 0 to 5% of plasticizer.
• MKT multilayer tubular structure
• one of the outer layers has a large proportion of plasticizer such as 15% by weight, but in this case, the proportion of plasticizer is compensated by the thickness of the layer which is then much thinner so that the average value of plasticizer present in all the inner layers does not exceed 5%.
• the proportion of plasticizer in this layer can then be up to 15% but its thickness does not exceed 20% of the total thickness of the tube, preferably it does not exceed 200 ⁇ m.
• the present invention relates to a multilayer tubular structure (MLT) comprising a layer (3) as defined above, in which at least a second outer layer (3 ') located above the barrier layer is present, and preferably located above the layer (3), said layer (3 ') being plasticized, said plasticizer being present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer, the thickness of said layer (3 ') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 ⁇ m.
• MLT multilayer tubular structure
• Layer (3 '), like layer (3), comprises predominantly an aliphatic type polyamide, that is to say that said aliphatic type polyamide is present in a proportion of more than 50% by weight in layer (3') .
• the polyamide of the aliphatic type is linear and is not of the cycloaliphatic type.
• said polyamide of predominantly aliphatic type of the layer or layers (3 ′) also predominantly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer (s) (3 ') consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer (s) (3') is completely aliphatic.
• the present invention relates to a multilayer tubular structure (MLT), in which the layer (s) (3) comprises (comprise) up to 1.5% by weight of plasticizer, by relative to the total weight of the composition of said layer or of all the compositions of the layers (3).
• the multilayer tubular structure comprises a single layer (3) and is devoid of plasticizer.
• the multilayer tubular structure comprises a single layer (3) and a single layer (2), the layers (2) and (3) being devoid of plasticizer.
• the present invention relates to a multilayer tubular structure (MLT), in which the level of plasticizer of all the layers located above the barrier layer is at most 5% by weight based on the total weight. compositions of all layers located above the barrier layer.
• MLT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT), in which the layer (3 ') is the outermost and is the only plasticized, the layer (s) (3) being plasticizer (s).
• MLT multilayer tubular structure
• the proportion of plasticizer can represent up to 15% by weight of the total weight of the composition of the layer (3 ′).
• Layer (4) when it is not a binder layer is an aliphatic type polyamide as defined for layers (2), (3) and (3 ').
• the tubular structure of the invention is a four-layer structure made up from the outside to the inside of the following layers: (3) // (4) // (1) // (2), the ( 3) being plasticized up to 15% as above and thin and the layer (4) when it is different from the binder layer as defined above is devoid of plasticizer as well as the layer (2).
• the tubular structure of the invention is a four-layer structure made up from the outside to the inside of the following layers: (3) // (1) // (4) // (2), the ( 3) being plasticized up to 15% by weight as above and preferably thin and the layer (4) when it is different from the binder layer, as defined above, is devoid of plasticizer as well as the layer (2).
• this layer (3) plasticized up to 15% by weight must not be too thin otherwise the barrier layer is too little in the center and the MLT structure may not be good enough in impact.
• Another layer (2 ') and / or a layer (3') may also be present in these two types of four-layer structures.
• the said layer (4) can also be a binder as described, in particular in the patents EP 1452307 and EP1162061 , EP 1216826 and EP0428833 .
• the binder layer is intended to be interposed between two layers which do not adhere to each other with difficulty.
• the binder can be for example, but without being limited to these, a composition based on 50% of copolyamide 6/12 (of ratio 70/30 by mass) of Mn 16000, and of 50% copolyamide 6/12 ( of ratio 30/70 by mass) of Mn 16000, a composition based on PP (polypropylene) grafted with maleic anhydride, known under the name Admer QF551A from the company Mitsui, a composition based on PA610 (from Mn 30,000, and as defined elsewhere) and 36% PA6 (from Mn 28000) and 1.2% organic stabilizers (consisting of 0.8% of Lowinox 44B25 phenol from Great Lakes, 0.2% of Irgafos 168 phosphite from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba), a composition based on PA612 (from Mn 29000, and as defined elsewhere) and of 36% of PA6 (of Mn 28000, and as defined elsewhere)
• the layer (4 ') may or may not contain a plasticizer.
• it is devoid of plasticizer just like the layer (2) and the layer (4), the layer (3) being plasticized but thin as defined above.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the polyamide of the inner layer (2) or the polyamide of the outer layer (3) is a fully polyamide.
• the polyamide of the inner layer (2) or the polyamide of the outer layer (3) is a fully polyamide.
• aliphatic preferably the polyamide of the inner layer (2) and the polyamide of the outer layer (3) are fully aliphatic polyamides.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which a second barrier layer (5) is present, said second barrier layer (5) being adjacent or not to the first barrier layer (1) and located below said barrier layer (1).
• MLT multilayer tubular structure
• This second barrier layer is different from the first barrier layer (1).
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the EVOH is an EVOH comprising up to 27% ethylene.
• MHT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the EVOH is an EVOH comprising an impact modifier.
• MHT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is a polyphthalamide (PPA) layer.
• MLT multilayer tubular structure
• PPA polyphthalamide
• PPA signifies a composition based mainly on a polyamide comprising a majority of units which comprise at least one aromatic monomer, in particular polyphthalamide of the type of copolyamide 6.T / x (or x designates one or more comonomoers) such as Zytel HTN from the company Dupont, such as Grivory HT from the company Ems, such as Amodel from the company Solvay, such as Genestar from the company Kuraray, such as PPA compositions based on coPA6T / 6I , coPA6T / 66, coPA6T / 6, coPA6T / 6I / 66, PPA9T, coPPA9T / x, PPA10T, coPPA10T / x.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is a fiber layer.
• MLT multilayer tubular structure
• the barrier layer (1) is an EVOH layer
• the second barrier layer (5) is a fiber layer.
• PPA or fluoropolymer, in particular of ETFE, EFEP, CPT type.
• the barrier layer (1) is an EVOH layer and the second barrier layer (5) is a PPA layer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is a fiber layer.
• MLT multilayer tubular structure
• the barrier layer (1) is an EVOH layer
• the second barrier layer (5) is a fiber layer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is a fiber layer.
• fluoropolymer in particular of ETFE, EFEP, CPT type.
• the polyamide of the inner layer (2) is a composition based on a polyamide chosen from A, B or C as defined above, in in particular PA6, PA66, PA6 / 66, PA11, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
• the polyamide of the outer layer (3) is a polyamide chosen from B or C as defined above, in particular PA 11, PA12, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
• the polyamide of the inner layer (2) is a composition based on a polyamide chosen from A, B or C as defined above, in in particular PA6, PA66, PA6 / 66, PA11, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed
• the polyamide of the outer layer (3) is a polyamide chosen from B or C as defined above, in particular PA 11, PA12, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, polyamides obtained from a lactam being advantageously washed.
• the present invention relates to a multilayer tubular structure (MLT) as defined below, in which the polyamide of the inner layer (2) or of at least one of the other layers (2) is a conductive polyamide.
• MKT multilayer tubular structure
• the conductive layer is that which is most internally, that is to say in contact with the fluid.
• the polyamide of layer (4) and / or (4 ') is a mixture of a polyamide having an average number of carbon atoms per atom of nitrogen of 10 or more and a polyamide having an average number of carbon atoms per nitrogen atom of 6 or less, for example PA12 and PA6 and an anhydride functionalized (co) polyolefin.
• the polyamide of layer (4) and / or (4 ') is chosen from binary mixtures: PA6 and PA12, PA6 and PA612, PA6 and PA610 , PA12 and PA612, PA12 and PA610, PA1010 and PA612, PA1010 and PA610, PA1012 and PA612, PA1012 and PA610, and ternary mixtures: PA6, PA610 and PA12; PA6, PA612 and PA12; PA6, PA614 and PA12.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one of the layers (2), (3), (3 '), (4) and ( 4 ') comprises at least one impact modifier and / or at least one additive.
• MLT multilayer tubular structure
• the impact modifier or the additive is not a plasticizer.
• the layers (2) and (3) comprise at least one impact modifier and / or at least one additive.
• the layers (2), (3) and (3 ') comprise at least one impact modifier and / or at least one additive.
• the layers (2), (3), (3 ') and (4) comprise at least one impact modifier and / or at least one additive.
• the layers (2), (3), (3 '), (4) and (4') comprise at least one impact modifier and / or at least one additive.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises the layers in the following order: (3 ') // (3) // (4') // (1) // (4) // (2) in which layers (3) and (3 ') are as defined above, the layer (2) and (4) not containing more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) and / or (4) is (are) devoid of plasticizer, the layer (4 ') comprising plasticizer, in particular the layer (4') is devoid of plasticizer.
• MKT multilayer tubular structure
• said layer (3 ') of the above six-layer structure is plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer , the thickness of said layer (3 ') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 ⁇ m, in particular the layer (3') is the outermost and is the only plasticized, the layer (s) (3) being devoid of plasticizer.
• the present invention relates to the use of a multilayer tubular MLT structure, as defined above, for the transport of fluids, in particular gasoline.
• the present invention relates to the use of an MLT multilayer tubular structure as defined above, to satisfy an extractable test, said test consisting in particular of filling said MLT multilayer tubular structure with alcoholic gasoline.
• FAM-B type and heating the whole to 60 ° C for 96 hours, then emptying it by filtering it into a beaker, then allowing the filtrate from the beaker to evaporate at room temperature to finally weigh this residue, the proportion of which must be less than or equal to approximately 6g / m2 internal tube surface.
• An extractable value less than or equal to approximately 6 g / m2 of internal tube surface indicates that the proportion of extractables is very low and will thus avoid clogging the injectors.
• Multilayer pipes are produced by coextrusion.
• An industrial McNeil multilayer extrusion line is used, equipped with 5 extruders, connected to a multilayer extrusion head with spiral mandrels.
• the 5 extruder configuration is used to make tubes ranging from 2 layers to 5 layers. In the case of structures with a number of layers less than 5, several extruders are then supplied with the same material. In the case of structures comprising 6 layers, an additional extruder is connected and a spiral mandrel is added to the existing head, with a view to making the internal layer, in contact with the fluid.
• the extruded materials Before the tests, in order to ensure the best tube properties and good extrusion quality, it is checked that the extruded materials have a residual moisture level before extrusion of less than 0.08%. Otherwise, an additional step of drying the material is carried out before the tests, generally in a vacuum dryer, for 1 night at 80 ° C.
• the tubes which meet the characteristics described in the present patent application, were taken, after stabilization of the extrusion parameters, the dimensions of the tubes referred to no longer changing over time.
• the diameter is controlled by a laser diameter gauge installed at the end of the line.
• the line speed is typically 20m / min. It generally varies between 5 and 100m / min.
• the screw speed of the extruders depends on the thickness of the layer and the diameter of the screw as is known to those skilled in the art.
• the temperature of the extruders and the tools must be adjusted so as to be sufficiently higher than the melting temperature of the compositions considered, so that they remain in the molten state, thus avoiding they solidify and block the machine.
• Extractables consisting of a tube filled with alcoholic essence of FAM-B type at 60 ° C, for 96 hours, then emptied and filtered into a beaker which is then allowed to evaporate and the residue of which is weighed, the latter having to be less than or equal to 6g / m2 (internal tube surface) ⁇ 4.5 g / m 2 of tube surface (internal internal surface) 4.5-5.5 g / m 2 of tube surface (internal internal surface) 5.5-6 g / m 2 of tube surface (internal internal surface) > 6 g / m 2 of tube surface (internal internal surface) VW shock-40 ° C standard VW TL52435 2010 ⁇ 4% breakage ⁇ 11% breakage ⁇ 21% breakage > 2
• the instantaneous permeability is zero during the induction period, then it increases progressively to a value at equilibrium which corresponds to the value of permeability in steady state. This value obtained in steady state is considered to be the permeability of the material.
• PA12-TL denotes a composition based on polyamide 12 of Mn (number molecular mass) 35,000, containing 6% of plasticizer BBSA (benzyl butyl sulfonamide), and 6% of EPR functionalized anhydride Exxelor VA1801 (company Exxon), and 1.2% organic stabilizers (consisting of 0.8% of Lowinox 44B25 phenol from Great Lakes, 0.2% of Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba). The melting point of this composition is 175 ° C.
• PA12-NoPlast PA12-TL without the plasticizer (the latter is replaced by the same% in PA12)
• Organic stabilizer 1.2% organic stabilizers consisting of 0.8% phenol (Lowinox 44B25 from the company Great Lakes), 0.2% phosphite (Irgafos 168 from the company Ciba, 0.2% anti-UV (Tinuvin 312 from the Ciba company).
• Plasticizer BBSA (benzyl butyl sulfonamide)
• Binder Composition based on 43.8% PA612 (tq defined elsewhere), 25% PA6 (tq defined elsewhere) and 20% impact modifier type EPR1, and 1.2% organic stabilizers (consisting of 0.8% of phenol Lowinox 44B25 from the company Great Lakes, 0.2% phosphite Irgafos 168 from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba), and 10% plasticizer BBSA (benzyl butyl sulfonamide).
• Binder-NoPlast Composition based on 48.8% PA612 (tq defined elsewhere), 30% PA6 (tq defined elsewhere), and 20% of impact modifier type EPR1, and 1.2% of organic stabilizers (consisting of 0.8% Lowinox 44B25 phenol from Great Lakes, 0.2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba).
• Binder2 Composition based on 43.8% PA610 (tq defined elsewhere), 25% PA6 (tq defined elsewhere) and 20% impact modifier type EPR1, and 1.2% organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from the company Great Lakes, 0.2% phosphite Irgafos 168 from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba), and 10% plasticizer BBSA (benzyl butyl sulfonamide).
• Binder PA610 + PA6 Designates a composition based on PA612 (of Mn 29000, and as defined elsewhere) and of 36% of PA6 (of Mn 28000, and as defined elsewhere) and of 1.2% of organic stabilizers (consisting of 0.8% of phenol Lowinox 44B25 from the company Great Lakes, 0.2% phosphite Irgafos 168 from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba).
• the structures having layers devoid of plasticizer located under the barrier and in particular in contact with the fluid exhibit excellent results on the extractables test and much better than the counter examples in which the layer in contact with the fluid is plasticized.

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